Liquid hard-surface cleaning compositions

ABSTRACT

A fabric softening product which is a composition or an article for application to fibrous materials so that a fabric softening component thereof is deposited on the fibrous materials and softens the same, the fabric softening component comprising at least one higher aliphatic acid ester selected from the group consisting of: I) an ester having formula (a) wherein R 1 , R 2 , R 3  and R 4  may be the same or different and are H, —(—CH 2 ) x OR 5  or —(—CH 2 ) y CH 3 ; R 5  is H, —OCR 6 , -|-(—CH 2 —)— m O-|- n H or -|-(—CH 2 —)— m O-|- n OCR 6  and —OCR 6  is a higher fatty acid acyl group having 8 to 24 carbon atoms; x is an integer from 0 to 3, y is an integer from 0 to 4, m is an integer from 1 to 3, and n is an integer from 1 to 10; with the proviso (1) that only two of R 1 , R 2 , R 3  and R 4  may be H or —(—CH 2 ) y CH 3  and (2) that there be at least 2 higher fatty acid acyl groups; II) an oligomer of I); and III) an ester having the formula: R 7 —O-|-(—CH 2 —)— a O-|- b  R 8  wherein R 7  and R 8  may be the same or different and are H or —OCR 6 , a is an integer from 1 to 3, b is an integer from 1 to 20 and —OCR 6  has the meaning ascribed above; with the proviso that only one of R 7  and R 8  may be H; and a dispersing agent therefor.

TECHNICAL FIELD

The present invention relates to liquid compositions for cleaninghard-surfaces.

BACKGROUND OF THE INVENTION

Liquid compositions for cleaning hard-surfaces have been disclosed inthe art. Much of the focus for such compositions has been on providingoutstanding cleaning on a variety of surfaces and soils. However, suchcompositions are not fully satisfactory from a consumer viewpoint,especially regarding the soil release properties imparted to thehard-surfaces treated therewith. Indeed, consumers are looking forliquid cleaning compositions, whereby next-time (subsequent) cleaning ismore facilitated. The object of the present invention is to formulate aliquid cleaning composition for removal of various soils fromhard-surfaces, that will facilitate the next-time cleaning operation.

It has now been found that the next-time cleaning performance isimproved when a hard-surface has first been treated with a liquidcomposition comprising particular antiresoiling ingredients, namely apolyalkoxylene glycol diester as defined herein, as a firstantiresoiling ingredient, together with a vinylpyrrolidone homopolymeror copolymer, as a second antiresoiling ingredient. Indeed, thecompositions of the present invention allow improved next-time cleaningperformance, as compared to the same compositions comprising only one ofsaid antiresoiling ingredients as defined herein, at the same totallevel of antiresoiling ingredients, or another antiresoiling polymericingredient like for example poly (trimethyl aminoethyl) methacrylate atthe same total level of antiresoiling ingredients.

More particularly, it has surprisingly been found that the use of such apolyalkoxylene glycol diester, as defined herein, together with such avinylpyrrolidone homopolymer or copolymer, such as a quaternized orunquaternized vinylpyrrolidone/dialkylaminoalkyl acrylate ormethacrylate copolymer, results in a synergistic effect on next-timecleaning performance.

Advantageously, the compositions herein may be used to cleanhard-surfaces made of a variety of materials like glazed and non-glazedceramic tiles, vinyl, no-wax vinyl, linoleum, melamine, glass, plastics,plastified wood, both in neat and diluted conditions, e.g., up to adilution level of 1:400 (composition:water).

A further advantage of the present invention is that the next-timecleaning performance is obtained with the compositions according to thepresent invention on various types of stains/soils including typicalgreasy stains like kitchen grease and other tough stains such asburnt/sticky food residues typically found in kitchens, while deliveringgood gloss to said surfaces.

Another advantage associated to the compositions according to thepresent invention comprising the polyalkoxylene glycol diester andvinylpyrrolidone homopolymer or copolymer, is that they have the abilityto provide good shine to the surface they have cleaned. Indeed, lessformation of watermarks and/or even limescale deposits are observed on asurface having been cleaned with the compositions of the presentinvention and later comes in contact with water, for example, during arinse operation. Advantageously, the shine benefit delivered to thesurface even persists after several cycles of rinsing, thus providinglong lasting protection against formation of watermarks and/or evenlimescale deposits on the surface, and hence long lasting shinysurfaces. Another advantage of the liquid compositions of the presentinvention is that not only next-time cleaning performance is improved,but that also good first time cleaning performance is delivered. Yet afurther advantage of the compositions of the present invention is thatfaster drying is obtained on the surfaces that have been cleanedtherewith, this both when used diluted or when used neat. In otherwords, the housewife will have the advantage to shorten the total timeof the cleaning operation of hard-surfaces and diminish theinconvenience of having wet floors in her home.

BACKGROUND ART

WO 94/26858 discloses a liquid hard-surface composition (pH 2-8) withnonionic surfactants (1-30%) and anionic polymers having an averagemolecular weight of less than 1,000,000, said polymers being free ofquaternary nitrogen groups. Said compositions bring initial cleaningbenefit in addition to the anti-soiling benefit. Indeed, WO 94/26858discloses that acrylic, methacrylic and maleic anhydride derivativessuch as copolymers of styrene with maleic produce a streak-free finishafter drying. No liquid compositions comprising a combination of apolyalkoxylene glycol diester together with a vinylpyrrolidonehomopolymer or copolymer are disclosed.

EP-A-635 567 discloses liquid compositions for cleaning solid surfacescomprising a cleaning agent capable of being deposited on the surfaceduring cleaning and of forming a dried layer adhered to the surface,said layer having a cohesive strength such that at least outermostsurface portion of the layer is removable by further washing.Polyvinylpyrrolidone is disclosed. However, no polyalkoxylene glycoldiesters are disclosed.

SUMMARY OF THE INVENTION

The present invention encompasses a liquid hard-surface cleaningcomposition comprising a polyalkoxylene glycol diester according to theformula:

wherein the substituents R₁ and R₂ each independently are substituted orunsubstituted, saturated or unsaturated, linear or branched hydrocarbonchains having from 1 to 36 carbon atoms and wherein n is an integer from10 to 400, and a vinylpyrrolidone homopolymer or copolymer.

The present invention also encompasses a process of cleaninghard-surfaces wherein a liquid composition as defined herein above, iscontacted with said surfaces.

DETAILED DESCRIPTION OF THE INVENTION

The Liquid Compositions:

As a first essential ingredient, the compositions according to thepresent invention comprise a polyalkoxylene glycol diester or a mixturethereof, as defined herein after.

Typically, the compositions of the present invention comprise from0.001% to 20% by weight of the total composition of said polyalkoxyleneglycol diester or a mixture thereof, preferably from 0.01% to 10%, morepreferably from 0.1% to 5% and most preferably from 0.2% to 2%.

Suitable polyalkoxylene glycol diesters for use herein have thefollowing formula:

in this formula the substituents R₁ and R₂ each independently aresubstituted or unsubstituted, saturated or unsaturated, linear orbranched hydrocarbon chains having from 1 to 36 carbon atoms, and n isan integer of from 10 to 400.

Preferably R₁ and R₂ each independently are substituted orunsubstituted, linear or branched alkyl groups or alkenyl groups havingfrom 1 to 36 carbon atoms, preferably from 1 to 30, more preferably from1 to 24, even more preferably from 1 to 22 and most preferably from 1 to18, or aryl groups having up to 36 carbon atoms, preferably from 6 to36, more preferably from 6 to 30. Preferably n is an integer from 20 to400, more preferably from 40 to 300, even more preferably from 40 to 200and most preferably from 40 to 150.

The preferred polyalkoxylene glycol diesters for use according to thepresent invention have a molecular weight of at least 200, morepreferably from 400 to 10,000 and most preferably from 800 to 6,000.

Suitable polyalkoxylene glycol diesters for use herein includeO′O-distearyl polyethylene glycol diester (MW 6000) or O′O-dioleylpolyethylene glycol diester (MW 560).

Such polyalkoxylene glycol diesters may be commercially available fromAkzo Nobel under the name KESSCO PEG 600ODS®, or from Lonza under thename Pegosperse® or from Huls under the name Marlosol FS®.

As a second essential ingredient, the compositions according to thepresent invention comprise a vinylpyrrolidone homopolymer or copolymeror a mixture thereof.

Typically, the compositions of the present invention comprise from0.001% to 20% by weight of the total composition of a vinylpyrrolidonehomopolymer or copolymer or a mixture thereof, preferably from 0.01% to10%, more preferably from 0.1% to 5% and most preferably from 0.2% to2%.

Suitable vinylpyrrolidone homopolymers for use herein is an homopolymerof N-vinylpyrrolidone having the following repeating monomer:

wherein n (degree of polymerisation) is an integer of from 10 to1,000,000 preferably from 20 to 100,000, and more preferably from 20 to10,000.

Accordingly, suitable vinylpyrrolidone homopolymers (“PVP”) for useherein have an average molecular weight of from 1,000 to 100,000,000,preferably from 2,000 to 10,000,000, more preferably from 5,000 to1,000,000, and most preferably from 50,000 to 500,000.

Suitable vinylpyrrolidone homopolymers are commercially available fromISP Corporation, New York, N.Y. and Montreal, Canada under the productnames PVP K-15® (viscosity molecular weight of 10,000), PVP K-30®(average molecular weight of 40,000), PVP K-60® (average molecularweight of 160,000), and PVP K-90® (average molecular weight of 360,000).Other suitable vinylpyrrolidone homopolymers which are commerciallyavailable from BASF Cooperation include Sokalan HP 165® and Sokalan HP12®; vinylpyrrolidone homopolymers known to persons skilled in thedetergent field (see for example EP-A-262,897 and EP-A-256,696).

Suitable copolymers of vinylpyrrolidone for use herein includecopolymers of N-vinylpyrrolidone and alkylenically unsaturated monomersor mixtures thereof.

The alkylenically unsaturated monomers of the copolymers herein includeunsaturated dicarboxylic acids such as maleic acid, chloromaleic acid,fumaric acid, itaconic acid, citraconic acid, phenylmaleic acid,aconitic acid, acrylic acid, N-vinylimidazole and vinyl acetate. Any ofthe anhydrides of the unsaturated acids may be employed, for exampleacrylate, methacrylate. Aromatic monomers like styrene, sulphonatedstyrene, alpha-methyl styrene, vinyl toluene, t-butyl styrene andsimilar well known monomers may be used.

The molecular weight of the copolymer of vinylpyrrolidone is notespecially critical so long as the copolymer is water-soluble, has somesurface activity and is adsorbed to the hard-surface from the liquidcomposition or solution (i.e. under dilute usage conditions) comprisingit in such a manner as to increase the hydrophilicity of the surface.However, the preferred copolymers of N-vinylpyrrolidone andalkylenically unsaturated monomers or mixtures thereof, have a molecularweight of between 1,000 and 1,000,000, preferably between 10,000 and500,000 and more preferably between 10,000 and 200,000.

For example particularly suitable N-vinylimidazole N-vinylpyrrolidonepolymers for use herein have an average molecular weight range from5,000-1,000,000, preferably from 5,000 to 500,000, and more preferablyfrom 10,000 to 200,000. The average molecular weight range wasdetermined by light scattering as described in Barth H. G. and Mays J.W. Chemical Analysis Vol 113, “Modern Methods of PolymerCharacterization”.

Such copolymers of N-vinylpyrrolidone and alkylenically unsaturatedmonomers like PVP/vinyl acetate copolymers are commercially availableunder the trade name Luviskol® series from BASF.

Particular preferred copolymers of vinylpyrrolidone for use in thecompositions of the present invention are quaternized or unquaternizedvinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymers.

The vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylatecopolymers (quaternised or unquaternised) suitable for use in thecompositions of the present invention are according to the followingformula:

in which n is between 20 and 99 and preferably between 40 and 90 mol %and m is between 1 and 80 and preferably between 5 and 40 mol %; R₁represents H or CH₃; y denotes 0 or 1; R₂ is —CH₂—CHOH—CH₂— orC_(x)H_(2x), in which x=2 to 18; R₃ represents a lower alkyl group offrom 1 to 4 carbon atoms, preferably methyl or ethyl, or

R₄ denotes a lower alkyl group of from 1 to 4 carbon atoms, preferablymethyl or ethyl; X⁻ is chosen from the group consisting of Cl, Br, I,1/2SO₄, HSO₄ and CH₃SO₃. The polymers can be prepared by the processdescribed in French Pat. Nos. 2,077,143 and 2,393,573.

The preferred quaternized or unquaternizedvinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylate copolymersfor use herein have a molecular weight of between 1,000 and 1,000,000,preferably between 10,000 and 500,000 and more preferably between 10,000and 100,000.

Such vinylpyrrolidone/dialkylaminoalkyl acrylate or methacrylatecopolymers are commercially available under the name copolymer 845®,Gafquat 734®, or Gafquat 755® from ISP Corporation, New York, N.Y. andMontreal, Canada or from BASF under the tradename Luviquat®.

Most preferred herein is quaternized copolymers of vinyl pyrrolidone anddimethyl aminoethymethacrylate (polyquaternium-11) available from BASF.

The present invention is based on the finding that the liquidcompositions of the present invention provide improved next-timecleaning performance when a hard-surface has been first treatedtherewith. Although not wishing to be bound by theory, it is speculatedthat the first antiresoiling ingredient, i.e., polyalkoxylene glycoldiester, and the second antiresoiling ingredient, i.e., vinylpyrrolidonehomopolymer or copolymer, have in common the property of adsorbing to ahard-surface being first cleaned therewith, in such a manner that ahygroscopic layer is left behind. The resulting hygroscopic layer canattract and retain ambient atmospheric water vapor to more effectivelyreduce adhesion of soils once treated and/or facilitate removal of soilssubsequently deposited thereon, i.e. less work (e.g. less scrubbingand/or wiping and/or less chemical action) is required to remove thesoils in the next-time cleaning operation, as compared to a similarsoiled hard-surface which has been first cleaned with the samecompositions without the first or second antiresoiling ingredientsaccording to the present invention.

More particularly, it has surprisingly been found that there is asynergistic effect on next-time cleaning performance associated with theuse of such a polyalkoxylene glycol diester and a vinylpyrrolidonehomopolymer or copolymer, as defined herein. Indeed, the next-timecleaning performance delivered by combining a polyalkoxylene glycoldiester and a vinylpyrrolidone homopolymer or copolymer, as definedherein, in a liquid composition, is superior than the next-time cleaningperformance delivered by for example the same composition, butcomprising only one of those ingredients at the same total level ofantiresoiling ingredients.

In a preferred embodiment of the compositions of the present inventionthe polyalkoxylene glycol diester as defined herein, and thevinylpyrrolidone homopolymer or copolymer, as defined herein, arepresent at a weight ratio of the polyalkoxylene glycol diester to thevinylpyrrolidone homopolymer or copolymer of from 1:100 to 100:1,preferably from 1:10 to 10:1 and more preferably from 1:2 to 2:1.

Also an advantage of the present invention is that effective next-timecleaning performance can be obtained at low total level of antiresoilingingredients. In a preferred embodiment the compositions herein comprisefrom 0.1% to 10% by weight of the total composition of thepolyalkoxylene glycol diester, and the vinylpyrrolidone homopolymer orcopolymer, preferably from 0.2% to 5%, more preferably from 0.3% to 2%and most preferably from 0.3% to 1.5%. Surprisingly, effective next-timecleaning performance is delivered not only when a composition of thepresent invention is contacted to the hard-surface to clean in its neatform, but also in its diluted form, e.g. up to a dilution level water:composition (400:1).

An advantage of the compositions of the present invention is that thefirst time cleaning performance is also increased, as compared forexample to the same compositions without said vinylpyrrolidonehomopolymer or copolymer.

By “cleaning performance”, it is meant herein cleaning on various typesof soils including greasy soils, like kitchen grease or burnt/stickyfood residues typically found in a kitchen (e.g., burnt milk) and thelike.

The first time dilute cleaning performance may be evaluated by thefollowing test method: Tiles of enamel, vinyl or ceramic are prepared byapplying to them a representative grease/particulate artificial soil,followed by aging. The test compositions and the reference compositionare diluted (e.g., composition:water 1:50 or 1:100), applied to asponge, and used to clean the tiles with a Sheen scrub tester. Thenumber of strokes required to clean to 100% clean is recorded. A minimumof 6 replicates can be taken with each result being generated induplicate against the reference on each soiled tile.

The next-time dilute cleaning performance may be evaluated by thefollowing test method: Following the procedure detailed for first timecleaning the tiles used for this previous test are taken and resoileddirectly without first being further washed or rinsed. The cleaningprocedure is then repeated using the Sheen scrub tester, taking carethat the test compositions are used to clean the same part of the tileas was previously cleaned by them. The number of strokes required toclean to 100% clean is recorded. A minimum of 6 replicates can be takenwith each result being generated in duplicate against the reference oneach soiled tile. This resoiling and cleaning procedure can be repeatedup to 5 times.

The test method for evaluating neat cleaning performance is identical toabove except that the test compositions and reference are used undilutedand that after cleaning a rinsing cycle is performed with clean water.This rinsing cycle may be repeated up to 5 times prior to the resoilingstep for next time cleaning evaluation.

Another advantage of the compositions of the present invention is thatthese compositions when applied on the surface to be cleaned either intheir neat or diluted form dry faster than the same compositionscomprising only the first or second antiresoiling ingredients asdescribed herein at the same total level of antiresoiling ingredients.Thus, the present invention also encompasses the use of a polyalkoxyleneglycol diester and vinylpyrrolidone homopolymer or copolymer, in aliquid composition, for faster evaporation of said composition when usedto clean a hard-surface in its diluted or neat form, and/or fasterevaporation of water subsequently coming into contact with said surfacefor rinsing off the surface after cleaning.

Although not wishing to be bound by theory, it has been observed thathard surfaces often have low affinity with water. This means that, whenwater gets in contact with hard-surfaces, its spreading, which iscontrolled by the interfacial energy (i.e., solid/liquid surfacetension), is very limited. Indeed, it has been observed that the moststable configuration for water is grouping in spherical droplets ratherthan forming a thin film uniformly spread over the surface. Thusrequiring more time to completely evaporate from said surface. It hasnow been found that when the polyalkoxylene glycol diester andvinylpyrrolidone homopolymer or copolymer are added together into aliquid hard-surface cleaning composition according to the presentinvention a hydrophilic layer is left on a hard-surface cleaned withsaid composition, said hydrophilic layer leaves the water coming incontact with the surface that has been first cleaned with saidcomposition (e.g., water which is used to rinse off the surfaces havingbeen so treated) uniformly spread over the surface (“sheeting effect”)instead of forming droplets. This way, the evaporation of thecomposition itself and subsequent water coming into contact with thesurface for example in the rinsing step is accelerated.

Not to be bound by theory, it is believed that the antiresoilingingredients described herein also have the ability to form a film on thesurface of the user skin, thereby providing improved skin mildness. Inanother embodiment, the present invention thus also encompasses the useof a polyalkoxylene glycol diester and/or polyvinyl pyrrolidonehomopolymer or copolymer, in a liquid composition, for improved skinmildness.

An additional advantage related to the use of the polyalkoxylene glycoldiester and/or polyvinyl pyrrolidone homopolymer or copolymer herein isthat, as they adhere on hard surface making them more hydrophilic, thesurfaces themselves become smoother (this can be perceived by touchingsaid surfaces) and this contributes to convey perception of surfaceperfectly cleaned.

The compositions according to the present invention particularlysuitable for the cleaning of a hard-surface are liquid compositions. Theliquid compositions of the present invention are preferably but notnecessarily formulated as aqueous compositions. Aqueous compositionstypically comprise from 50% to 99% by weight of the total composition ofwater, preferably from 60% to 95%, and more preferably from 80% to 95%.

The liquid compositions herein may be formulated in the full pH range of0 to 14, preferably 1 to 13. Typically, the compositions herein areformulated in a neutral to highly alkaline pH range from 7 to 12,preferably from 9 to 11 and more preferably from 9.5 to 11. The pH ofthe compositions herein can be adjusted by any of the means well-knownto those skilled in the art such as acidifying agents like organic orinorganic acids, or alkalinising agents like NaOH, KOH, K2CO3, Na2CO3and the like. Preferred organic acids for use herein have a pka of lessthan 6. Suitable organic acids are selected from the group consisting ofcitric acid, lactic acid, glycolic acid, succinic acid, glutaric acidand adipic acid and mixtures thereof. A mixture of said acids may becommercially available from BASF under the trade name Sokalan® DCS.

Optional Ingredients:

The liquid compositions according to the present invention may comprisea variety of optional ingredients depending on the technical benefitaimed for and the surface treated.

Suitable optional ingredients for use herein include surfactants,builders, chelants, polymers, solvents, buffers, bactericides,hydrotropes, colorants, stabilisers, radical scavengers, bleaches,bleach activators, suds controlling agents like fatty acids, enzymes,soil suspenders, dye transfer agents, brighteners, anti dusting agents,dispersants, dye transfer inhibitors, pigments, dyes and/or perfumes.

Surfactants

The liquid compositions of the present invention preferably comprise asurfactant, or mixtures thereof. Said surfactant may be present in thecompositions according to the present invention in amounts of from 0.1%to 50% by weight of the total composition, preferably of from 0.1% to20% and more preferably of from 1% to 10%.

Surfactants are desired herein as they further contribute to thecleaning performance and/or gloss benefit of the compositions of thepresent invention. Surfactants for use herein include nonionicsurfactants, anionic surfactants, cationic surfactants, amphotericsurfactants, zwitterionic surfactants, and mixtures thereof.Particularly preferred surfactants are the nonionic surfactants.Suitable nonionic surfactants for use herein include a class ofcompounds which may be broadly defined as compounds produced by thecondensation of alkylene oxide groups (hydrophilic in nature) with anorganic hydrophobic compound, which may be branched or linear aliphatic(e.g. Guerbet or secondary alcohols) or alkyl aromatic in nature. Thelength of the hydrophilic or polyoxyalkylene radical which is condensedwith any particular hydrophobic group can be readily adjusted to yield awater-soluble compound having the desired degree of balance betweenhydrophilic and hydrophobic elements. For example, a well-known class ofnonionic synthetic detergents is made available on the market under thetrade name “Pluronic”. These compounds are formed by condensing ethyleneoxide with an hydrophobic base formed by the condensation of propyleneoxide with propylene glycol. The hydrophobic portion of the moleculewhich, of course, exhibits water-insolubility has a molecular weight offrom about 1500 to 1800. The addition of polyoxyethylene radicals tothis hydrophobic portion tends to increase the water-solubility of themolecule as a whole and the liquid character of the products is retainedup to the point where polyoxyethylene content is about 50% of the totalweight of the condensation product.

Other suitable nonionic synthetic detergents include:

(i) The polyethylene oxide condensates of alkyl phenols, e.g., thecondensation products of alkyl phenols having an alkyl group containingfrom about 6 to 12 carbon atoms in either a straight chain or branchedchain configuration, with ethylene oxide, the said ethylene oxide beingpresent in amounts equal to 10 to 25 moles of ethylene oxide per mole ofalkyl phenol. The alkyl substituent in such compounds may be derivedfrom polymerized propylene, diisobutylene, octane, and nonane;

(ii) Those derived from the condensation of ethylene oxide with theproduct resulting from the reaction of propylene oxide and ethylenediamine products which may be varied in composition depending upon thebalance between the hydrophobic and hydrophilic elements which isdesired. Examples are compounds containing from about 40% to about 80%polyoxyethylene by weight and having a molecular weight of from about5000 to about 11000 resulting from the reaction of ethylene oxide groupswith a hydrophobic base constituted of the reaction product of ethylenediamine and excess propylene oxide, said base having a molecular weightof the order of 2500 to 3000;

(iii) The condensation product of aliphatic alcohols having from 8 to 18carbon atoms, in either straight chain or branched chain configuration,with ethylene oxide, e.g., a coconut alcohol ethylene oxide condensatehaving from 10 to 30 moles of ethylene oxide per mole of coconutalcohol, the coconut alcohol fraction having from 10 to 14 carbon atoms;

(iv) Trialkyl amine oxides and trialkyl phosphine oxides wherein onealkyl group ranges from 10 to 18 carbon atoms and two alkyl groups rangefrom 1 to 3 carbon atoms; the alkyl groups can contain hydroxysubstituents; specific examples are dodecyl di(2-hydroxyethyl)amineoxide and tetradecyl dimethyl phosphine oxide.

Also useful as a nonionic surfactant are the alkylpolysaccharidesdisclosed in U.S. Pat. No. 4,565,647, Llenado, issued Jan. 21, 1986,having a hydrophobic group containing from about 6 to about 30 carbonatoms, preferably from about 10 to about 16 carbon atoms andpolysaccharide, e.g., a polyglycoside, hydrophilic group containing fromabout 1.3 to about 10, preferably from about 1.3 to about 3, mostpreferably from about 1.3 to about 2.7 saccharide units. Any reducingsaccharide containing 5 or 6 carbon atoms can be used, e.g., glucose,galactose, and galactosyl moieties can be substituted for the glucosylmoieties. (Optionally the hydrophobic group is attached at the 2-, 3-,4-, etc. positions thus giving a glucose or galactose as opposed to aglucoside or galactoside.) The intersaccharide bonds can be, e.g.,between the one position of the additional saccharide units and the 2-,3-, 4-, and/or 6-positions of the preceding saccharide units.

Optionally, and less desirably, there can be a polyalkyleneoxide chainjoining the hydrophobic moiety and the polysaccharide moiety. Thepreferred alkyleneoxide is ethylene oxide. Typical hydrophobic groupsinclude alkyl groups, either saturated or unsaturated, branched orunbranched containing from about 8 to about 18, preferably from about 10to about 16, carbon atoms. Preferably, the alkyl group can contain up toabout 3 hydroxy groups and/or the polyalkyleneoxide chain can contain upto about 10, preferably less than 5, alkyleneoxide moieties. Suitablealkyl polysaccharides are octyl, nonyidecyl, undecyldodecyl, tridecyl,tetradecyl, pentadecyl, hexadecyl, heptadecyl, and octadecyl, di-, tri-,tetra-, penta-, and hexaglucosides, galactosides, lactosides, glucoses,fructosides, fructoses and/or galactoses. Suitable mixtures includecoconut alkyl, di-, tri-, tetra-, and pentaglucosides and tallow alkyltetra-, penta-, and hexaglucosides.

The preferred alkylpolyglycosides have the formula:

R²O(C_(n)H_(2n)O)_(t)(glucosyl)_(x)

wherein R² is selected from the group consisting of alkyl, alkylphenyl,hydroxyalkyl, hydroxyalkylphenyl, and mixtures thereof in which thealkyl groups contain from about 10 to about 18, preferably from about 12to about 14, carbon atoms; n is 2 or 3, preferably 2; t is from 0 toabout 10, preferably 0; and x is from about 1.3 to about 10, preferablyfrom about 1.3 to about 3, most preferably from about 1.3 to about 2.7.The glycosyl is preferably derived from glucose. To prepare thesecompounds, the alcohol or alkylpolyethoxy alcohol is formed first andthen reacted with glucose, or a source of glucose, to form the glucoside(attachment at the 1-position). The additional glycosyl units can thenbe attached between their 1-position and the preceding glycosyl units2-, 3-, 4- and/or 6-position, preferably predominantely the 2-position.

Although not preferred, the condensation products of ethylene oxide witha hydrophobic base formed by the condensation of propylene oxide withpropylene glycol are also suitable for use herein. The hydrophobicportion of these compounds will preferably have a molecular weight offrom about 1500 to about 1800 and will exhibit water insolubility. Theaddition of polyoxyethylene moieties to this hydrophobic portion tendsto increase the water solubility of the molecule as a whole, and theliquid character of the product is retained up to the point where thepolyoxyethylene content is about 50% of the total weight of thecondensation product, which corresponds to condensation with up to about40 moles of ethylene oxide. Examples of compounds of this type includecertain of the commercially available Pluronic™ surfactants, marketed byBASF.

Also not preferred, although suitable for use as nonionic surfactantsherein are the condensation products of ethylene oxide with the productresulting from the reaction of propylene oxide and ethylenediamine. Thehydrophobic moiety of these products consists of the reaction product ofethylenediamine and excess propylene oxide, and generally has amolecular weight of from about 2,500 to about 3,000. This hydrophobicmoiety is condensed with ethylene oxide to the extent that thecondensation product contains from about 40% to about 80% by weight ofpolyoxyethylene and has a molecular weight of from about 5,000 to about11,000. Examples of this type of nonionic surfactant include certain ofthe commercially available Tetronic™ compounds, marketed by BASF.

Other suitable nonionic surfactants for use herein include polyhydroxyfatty acid amides of the structural formula:

wherein: R¹ is H, C₁-C₄ hydrocarbyl, 2-hydroxy ethyl, 2-hydroxypropyl,or a mixture thereof, preferably C₁-C₄ alkyl, more preferably C₁ or C₂alkyl, most preferably C₁ alkyl (i.e., methyl); and R² is a C₅-C₃₁hydrocarbyl, preferably straight chain C₇-C₁₉ alkyl or alkenyl, morepreferably straight chain C₉-C₁₇ alkyl or alkenyl, most preferablystraight chain C₁₁-C₁₇ alkyl or alkenyl, or mixtures thereof; and Z is apolyhydroxyhydrocarbyl having a linear hydrocarbyl chain with at least 3hydroxyls directly connected to the chain, or an alkoxylated derivative(preferably ethoxylated or propoxylated) thereof. Z preferably will bederived from a reducing sugar in a reductive amination reaction; morepreferably Z is a glycityl. Suitable reducing sugards include glucose,fructose, maltose, lactose, galactose, mannose, and xylose. As rawmaterials, high dextrose corn syrup can be utilised as well as theindividual sugars listed above. These corn syrups may yield a mix ofsugar components for Z. It should be understood that it is by no meansintended to exclude other suitable raw materials. Z preferably will beselected from the group consisting of —CH₂—(CHOH)_(n)—CH₂OH,—CH(CH₂OH)—(CHOH)_(n−1)—CH₂OH, —CH₂—(CHOH)₂(CHOR′)(CHOH)—CH₂OH, where nis an integer from 3 to 5, inclusive, and R′ is H or a cyclic oraliphatic monosaccharide, and alkoxylated derivatives thereof. Mostpreferred are glycityls wherein n is 4, particularly —CH₂—(CHOH)₄—CH₂OH.

In Formula (I), R¹ can be, for example, N-methyl, N-ethyl, N-propyl,N-isopropyl, N-butyl, N-2-hydroxy ethyl, or N-2-hydroxy propyl. R²—CO—N<can be, for example, cocamide, stearamide, oleamide, lauramide,myristamide, capricamide, palmitamide, tallowamide, etc. Z can be1-deoxyglucityl, 2-deoxyfructityl, 1-deoxymaltityl, 1-deoxylactityl,1-deoxygalactityl, 1-deoxymannityl, 1-deoxymaltotriotityl, etc.

In one embodiment herein suitable nonionic surfactants for use hereinare polyethylene oxide condensates of alkyl phenols, condensationproducts of primary and secondary aliphatic alcohols with from about 1to about 25 moles of ethyelene oxide, alkylpolysaccharides, and mixturesthereof. Most preferred are C₈-C₁₄ alkyl phenol ethoxylates having from3 to 15 ethoxy groups and C₈-C₁₈ alcohol ethoxylates (preferably C₁₀avg.) having from 2 to 10 ethoxy groups, and mixtures thereof.

Particularly preferred surfactants include also the anionic surfactants.Suitable anionic surfactants for use herein include alkali metal (e.g.,sodium or potassium) fatty acids, or soaps thereof, containing fromabout 8 to about 24, preferably from about 10 to about 20 carbon atoms.

The fatty acids including those used in making the soaps can be obtainedfrom natural sources such as, for instance, plant or animal-derivedglycerides (e.g., palm oil, coconut oil, babassu oil, soybean oil,castor oil, tallow, whale oil, fish oil, tallow, grease, lard andmixtures thereof). The fatty acids can also be synthetically prepared(e.g., by oxidation of petroleum stocks or by the Fischer-Tropschprocess). Alkali metal soaps can be made by direct saponification offats and oils or by the neutralization of the free fatty acids which areprepared in a separate manufacturing process. Particularly useful arethe sodium and potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium and potassium tallow andcoconut soaps.

The term “tallow” is used herein in connection with fatty acid mixtureswhich typically have an approximate carbon chain length distribution of2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleic and 3% linoleic(the first three fatty acids listed are saturated). Other mixtures withsimilar distribution, such as the fatty acids derived from variousanimal tallows and lard, are also included within the term tallow. Thetallow can also be hardened (i.e., hydrogenated) to convert part or allof the unsaturated fatty acid moieties to saturated fatty acid moieties.When the term “coconut” is used herein it refers to fatty acid mixtureswhich typically have an approximate carbon chain length distribution ofabout 8% C8, 7% C10, 48% C12, 17% C14, 9% C16, 2% C18, 7% oleic, and 2%linoleic (the first six fatty acids listed being saturated). Othersources having similar carbon chain length distribution such as palmkernel oil and babassu oil are included with the term coconut oil.

Other suitable anionic surfactants for use herein include water-solublesalts, particularly the alkali metal salts, of organic sulfuric reactionproducts having in the molecular structure an alkyl radical containingfrom about 8 to about 22 carbon atoms and a radical selected from thegroup consisting of sulfonic acid and sulfuric acid ester radicals.Important examples of these synthetic detergents are the sodium,ammonium or potassium alkyl sulfates, especially those obtained bysulfating the higher alcohols produced by reducing the glycerides oftallow or coconut oil; sodium or potassium alkyl benzene sulfonates, inwhich the alkyl group contains from about 9 to about 15 carbon atoms,especially those of the types described in U.S. Pat. Nos. 2,220,099 and2,477,383, incorporated herein by reference; sodium alkyl glyceryl ethersulfonates, especially those ethers of the higher alcohols derived fromtallow and coconut oil; sodium coconut oil fatty acid monoglyceridesulfates and sulfonates; sodium or potassium salts of sulfuric acidesters of the reaction product of one mole of a higher fatty alcohol(e.g., tallow or coconut oil alcohols) and about three moles of ethyleneoxide; sodium or potassium salts of alkyl phenol ethylene oxide ethersulfates with about four units of ethylene oxide per molecule and inwhich the alkyl radicals contain about 9 carbon atoms; the reactionproduct of fatty acids esterified with isothionic acid and neutralizedwith sodium hydroxide where, for example, the fatty acids are derivedfrom coconut oil; sodium or potassium salts of fatty acid amide of amethyl taurine in which the fatty acids, for example, are derived fromcoconut oil; and others known in the art, a number being specificallyset forth in U.S. Pat. Nos. 2,486,921, 2,486,922 and 2,396,278,incorporated herein by reference.

Suitable zwitterionic detergents for use herein comprise the betaine andbetaine-like detergents wherein the molecule contains both basic andacidic groups which form an inner salt giving the molecule both cationicand anionic hydrophilic groups over a broad range of pH values. Somecommon examples of these detergents are described in U.S. Pat. Nos.2,082,275, 2,702,279 and 2,255,082, incorporated herein by reference.Preferred zwitterionic detergent compounds have the formula:

wherein R1 is an alkyl radical containing from 8 to 22 carbon atoms, R2and R3 contain from 1 to 3 carbon atoms, R4 is an alkylene chaincontaining from 1 to 3 carbon atoms, X is selected from the groupconsisting of hydrogen and a hydroxyl radical, Y is selected from thegroup consisting of carboxyl and sulfonyl radicals and wherein the sumof R1, R2 and R3 radicals is from 14 to 24 carbon atoms. Amphoteric andampholytic detergents which can be either cationic or anionic dependingupon the pH of the system are represented by detergents such asdodecylbeta-alanine, N-alkyltaurines such as the one prepared byreacting dodecylamine with sodium isethionate according to the teachingof U.S. Pat. No. 2,658,072, N-higher alkylaspartic acids such as thoseproduced according to the teaching of U.S. Pat. No. 2,438,091, and theproducts sold under the trade name “Miranol”, and described in U.S. Pat.No. 2,528,378, said patents being incorporated herein by reference.Additional synthetic detergents and listings of their commercial sourcescan be found in McCutcheon's Detergents and Emulsifiers, North AmericanEd. 1980, incorporated herein by reference.

Suitable amphoteric surfactants include the amine oxides correspondingto the formula:

RR′R″N→O

wherein R is a primary alkyl group containing 6-24 carbons, preferably10-18 carbons, and wherein R′ and R″ are, each, independently, an alkylgroup containing 1 to 6 carbon atoms. The arrow in the formula is aconventional representation of a semi-polar bond. The preferred amineoxides are those in which the primary alkyl group has a straight chainin at least most of the molecules, generally at least 70%, preferably atleast 90% of the molecules, and the amine oxides which are especiallypreferred are those in which R contains 10-18 carbons and R′ and R″ areboth methyl. Exemplary of the preferred amine oxides are theN-hexyldimethylamine oxide, N-octyldimethylamine oxide,N-decyldimethylamine oxide, N-dodecyl dimethylamine oxide,N-tetradecyidimethylamine oxide, N-hexadecyl dimethylamine oxide,N-octadecyldimethylamine oxide, N-eicosyldimethylamine oxide,N-docosyldimethylamine oxide, N-tetracosyl dimethylamine oxide, thecorresponding amine oxides in which one or both of the methyl groups arereplaced with ethyl or 2-hydroxyethyl groups and mixtures thereof. Amost preferred amine oxide for use herein is N-decyldimethylamine oxide.

Other suitable amphoteric surfactants for the purpose of the inventionare the phosphine or sulfoxide surfactants of formula:

RR′R″A→O

wherein A is phosphorus or sulfur atom, R is a primary alkyl groupcontaining 6-24 carbons, preferably 10-18 carbons, and wherein R′ and R″are, each, independently selected from methyl, ethyl and 2-hydroxyethyl.The arrow in the formula is a conventional representation of asemi-polar bond.

Cationic surfactants suitable for use in compositions of the presentinvention are those having a long-chain hydrocarbyl group. Examples ofsuch cationic surfactants include the ammonium surfactants such asalkyldimethylammonium halogenides, and those surfactants having theformula:

[R²(OR³)_(y)][R⁴(OR³)_(y)]₂R⁵N⁺X⁻

wherein R² is an alkyl or alkyl benzyl group having from 8 to 18 carbonatoms in the alkyl chain, each R³ is selected from the group consistingof —CH₂CH₂—, —CH₂CH(CH₃)—, —CH₂CH(CH₂OH)—, —CH₂CH₂CH₂—, and mixturesthereof; each R⁴ is selected from the group consisting of C₁-C₄ alkyl,C₁-C₄ hydroxyalkyl, benzyl ring structures formed by joining the two R⁴groups, —CH₂CHOH—CHOHCOR⁶CHOHCH₂OH wherein R⁶ is any hexose or hexosepolymer having a molecular weight less than about 1000, and hydrogenwhen y is not 0; R⁵ is the same as R⁴ or is an alkyl chain wherein thetotal number of carbon atoms of R² plus R⁵ is not more than about 18;each y is from 0 to about 10 and the sum of the y values is from 0 toabout 15; and X is any compatible anion.

Other cationic surfactants useful herein are also described in U.S. Pat.No. 4,228,044, Cambre, issued Oct. 14, 1980, incorporated herein byreference.

Perfumes

Suitable perfumes for use herein include materials which provide anolfactory aesthetic benefit and/or cover any “chemical” odour that theproduct may have. The main function of a small fraction of the highlyvolatile, low boiling (having low boiling points), perfume components inthese perfumes is to improve the fragrance odor of the product itself,rather than impacting on the subsequent odor of the surface beingcleaned. However, some of the less volatile, high boiling perfumeingredients provide a fresh and clean impression to the surfaces, and itis desirable that these ingredients be deposited and present on the drysurface. Perfume ingredients can be readily solubilized in thecompositions, for instance by the nonionic detergent surfactants. Theperfume ingredients and compositions suitable to be used herein are theconventional ones known in the art. Selection of any perfume component,or amount of perfume, is based solely on aesthetic considerations.

Suitable perfume compounds and compositions can be found in the artincluding U.S. Pat. No. 4,145,184, Brain and Cummins, issued Mar. 20,1979; U.S. Pat. No. 4,209,417, Whyte, issued Jun. 24, 1980; U.S. Pat.No. 4,515,705, Moeddel, issued May 7, 1985; and U.S. Pat. No. 4,152,272,Young, issued May 1, 1979, all of said patents being incorporated hereinby reference. In general, the degree of substantivity of a perfume isroughly proportional to the percentages of substantive perfume materialused. Relatively substantive perfumes contain at least about 1%,preferably at least about 10%, substantive perfume materials.Substantive perfume materials are those odorous compounds that depositon surfaces via the cleaning process and are detectable by people withnormal olfactory acuity. Such materials typically have vapour pressureslower than that of the average perfume material. Also, they typicallyhave molecular weights of about 200 and above, and are detectable atlevels below those of the average perfume material. Perfume ingredientsuseful herein, along with their odor character, and their physical andchemical properties, such as boiling point and molecular weight, aregiven in “Perfume and Flavor Chemicals (Aroma Chemicals),” SteffenArctander, published by the author, 1969, incorporated herein byreference.

Examples of the highly volatile, low boiling, perfume ingredients are:anethole, benzaldehyde, benzyl acetate, benzyl alcohol, benzyl formate,iso-bornyl acetate, camphene, ciscitral (neral), citronellal,citronellol, citronellyl acetate, para-cymene, decanal, dihydrolinalool,dihydromyrcenol, dimethyl phenyl carbinol, eucaliptol, geranial,geraniol, geranyl acetate, geranyl nitrile, cis-3-hexenyl acetate,hydroxycitronellal, d-limonene, linalool, linalool oxide, linalylacetate, linalyl propionate, methyl anthranilate, alpha-methyl ionone,methyl nonyl acetaldehyde, methyl phenyl carbinyl acetate, laevo-menthylacetate, menthone, iso-menthone, mycrene, myrcenyl acetate, myrcenol,nerol, neryl acetate, nonyl acetate, phenyl ethyl alcohol, alpha-pinene,beta-pinene, gamma-terpinene, alpha-terpineol, beta-terpineol, terpinylacetate, and vertenex (para-tertiary-butyl cyclohexyl acetate). Somenatural oils also contain large percentages of highly volatile perfumeingredients. For example, lavandin contains as major components:linalool; linalyl acetate; geraniol; and citronellol. Lemon oil andorange terpenes both contain about 95% of d-limonene. Examples ofmoderately volatile perfume ingredients are: amyl cinnamic aldehyde,iso-amyl salicylate, beta-caryophyllene, cedrene, cinnamic alcohol,coumarin, dimethyl benzyl carbinyl acetate, ethyl vanillin, eugenol,iso-eugenol, flor acetate, heliotropine, 3-cis-hexenyl salicylate, hexylsalicylate, lilial (para-tertiarybutyl-alpha-methyl hydrocinnamicaldehyde), gamma-methyl ionone, nerolidol, patchouli alcohol, phenylhexanol, beta-selinene, trichloromethyl phenyl carbinyl acetate,triethyl citrate, vanillin, and veratraldehyde. Cedarwood terpenes arecomposed mainly of alpha-cedrene, beta-cedrene, and other C15H24sesquiterpenes.

Examples of the less volatile, high boiling, perfume ingredients are:benzophenone, benzyl salicylate, ethylene brassylate, galaxolide(1,3,4,6,7,8-hexahydro-4,6,6,7,8,8-hexamethyl-cyclopenta-gama-2-benzopyran),hexyl cinnamic aldehyde, lyral (4-(4-hydroxy-4-methylpentyl)-3-cyclohexene-10-carboxaldehyde), methyl cedrylone, methyldihydro jasmonate, methyl-beta-naphthyl ketone, musk indanone, muskketone, musk tibetene, and phenylethyl phenyl acetate.

Selection of any particular perfume ingredient is primarily dictated byaesthetic considerations.

The compositions herein may comprise a perfume ingredient, or mixturesthereof, in amounts up to 5.0% by weight of the total composition,preferably in amounts of 0.1% to 1.5%.

Chelating Agents

Another class of optional compounds for use herein include chelatingagents or mixtures thereof. Chelating agents can be incorporated in thecompositions herein in amounts ranging from 0.0% to 10.0% by weight ofthe total composition, preferably 0.1% to 5.0%.

Suitable phosphonate chelating agents for use herein may include alkalimetal ethane 1-hydroxy diphosphonates (HEDP), alkylene poly (alkylenephosphonate), as well as amino phosphonate compounds, including aminoaminotri(methylene phosphonic acid) (ATMP), nitrilo trimethylenephosphonates (NTP), ethylene diamine tetra methylene phosphonates, anddiethylene triamine penta methylene phosphonates (DTPMP). Thephosphonate compounds may be present either in their acid form or assalts of different cations on some or all of their acid functionalities.Preferred phosphonate chelating agents to be used herein are diethylenetriamine penta methylene phosphonate (DTPMP) and ethane 1-hydroxydiphosphonate (HEDP). Such phosphonate chelating agents are commerciallyavailable from Monsanto under the trade name DEQUEST®.

Polyfunctionally-substituted aromatic chelating agents may also beuseful in the compositions herein. See U.S. Pat. No. 3,812,044, issuedMay 21, 1974, to Connor et al. Preferred compounds of this type in acidform are dihydroxydisulfobenzenes such as1,2-dihydroxy-3,5-disulfobenzene.

A preferred biodegradable chelating agent for use herein is ethylenediamine N,N′-disuccinic acid, or alkali metal, or alkaline earth,ammonium or substitutes ammonium salts thereof or mixtures thereof.Ethylenediamine N,N′-disuccinic acids, especially the (S,S) isomer havebeen extensively described in U.S. Pat. No. 4,704,233, Nov. 3, 1987, toHartman and Perkins. Ethylenediamine N,N′-disuccinic acids is, forinstance, commercially available under the tradename ssEDDS® from PalmerResearch Laboratories.

Suitable amino carboxylates for use herein include ethylene diaminetetra acetates, diethylene triamine pentaacetates, diethylene triaminepentaacetate (DTPA), N-hydroxyethylethylenediamine triacetates,nitrilotri-acetates, ethylenediamine tetrapropionates,triethylenetetraaminehexa-acetates, ethanol-diglycines, propylenediamine tetracetic acid (PDTA) and methyl glycine di-acetic acid (MGDA),both in their acid form, or in their alkali metal, ammonium, andsubstituted ammonium salt forms. Particularly suitable aminocarboxylates to be used herein are diethylene triamine penta aceticacid, propylene diamine tetracetic acid (PDTA) which is, for instance,commercially available from BASF under the trade name Trilon FS® andmethyl glycine di-acetic acid (MGDA).

Further carboxylate chelating agents for use herein include salicylicacid, aspartic acid, glutamic acid, glycine, malonic acid or mixturesthereof.

Builders:

The liquid compositions of the present invention may also comprises abuilder or a mixture thereof, as an optional ingredient. Suitablebuilders for use herein include polycarboxylates and polyphosphates, andsalts thereof. Typically, the compositions of the present inventioncomprise up to 20.0% by weight of the total composition of a builder ormixtures thereof, preferably from 0.1% to 10.0%, and more preferablyfrom 0.5% to 5.0%.

Suitable and preferred polycarboxylates for use herein are organicpolycarboxylates where the highest LogKa, measured at 25° C./0.1M ionicstrength is between 3 and 8, wherein the sum of the LogKCa+LogKMg,measured at 25° C./0.1M ionic strength is higher than 4, and whereinLogKCa=LogKMg±2 units, measured at 25° C./0.1M ionic strength.

Such suitable and preferred polycarboxylates include citrate andcomplexes of the formula:

CH(A)(COOX)—CH(COOX)—O—CH(COOX)—CH(COOX)(B)

wherein A is H or OH; B is H or —O—CH(COOX)—CH₂(COOX); and X is H or asalt-forming cation. For example, if in the above general formula A andB are both H, then the compound is oxydissuccinic acid and itswater-soluble salts. If A is OH and B is H, then the compound istartrate monosuccinic acid (TMS) and its water-soluble salts. If A is Hand B is —O—CH(COOX)—CH₂(COOX), then the compound is tartrate disuccinicacid (TDS) and its water-soluble salts. Mixtures of these builders areespecially preferred for use herein. Particularly TMS to TDS, thesebuilders are disclosed in U.S. Pat. No. 4,663,071, issued to Bush etal., on May 5, 1987.

Still other ether polycarboxylates suitable for use herein includecopolymers of maleic anhydride with ethylene or vinyl methyl ether,1,3,5-trihydroxy benzene-2,4,6-trisulfonic acid.

Other useful polycarboxylate builders include the etherhydroxypolycarboxylates represented by the structure:

HO—[C(R)(COOM)—C(R)(COOM)—O]_(n)—H

wherein M is hydrogen or a cation wherein the resultant salt iswater-soluble, preferably an alkali metal, ammonium or substitutedammonium cation, n is from about 2 to about 15 (preferably n is fromabout 2 to about 10, more preferably n averages from about 2 to about 4)and each R is the same or different and selected from hydrogen, C₁₋₄alkyl or C₁₋₄ substituted alkyl (preferably R is hydrogen).

Suitable ether polycarboxylates also include cyclic compounds,particularly alicyclic compounds, such as those described in U.S. Pat.Nos. 3,923,679; 3,835,163; 4,158,635; 4,120,874 and 4,102,903, all ofwhich are incorporated herein by reference.

Preferred amongst those cyclic compounds are dipicolinic acid andchelidanic acid.

Also suitable polycarboxylates for use herein are mellitic acid,succinic acid, polymaleic acid, benzene 1,3,5-tricarboxylic acid,benezene pentacarboxylic acid, and carboxymethyloxysuccinic acid, andsoluble salts thereof.

Still suitable carboxylate builders herein include the carboxylatedcarbohydrates disclosed in U.S. Pat. No. 3,723,322, Diehl, issued Mar.28, 1973, incorporated herein by reference.

Other suitable carboxylates for use herein, but which are less preferredbecause they do not meet the above criteria are alkali metal, ammoniumand substituted ammonium salts of polyacetic acids. Examples ofpolyacetic acid builder salts are sodium, potassium, lithium, ammoniumand substituted ammonium salts of ethylenediamine, tetraacetic acid andnitrilotriacetic acid.

Other suitable, but less preferred polycarboxylates are those also knownas alkyliminoacetic builders such as methyl imino diacetic acid, alaninediacetic acid, methyl glycine diacetic acid, hydroxy propylene iminodiacetic acid and other alkyl imino acetic acid builders.

Also suitable in the compositions of the present invention are the3,3-dicarboxy-4-oxa-1,6-hexanediotes and the related compounds disclosedin U.S. Pat. No. 4,566,984, Bush, issued Jan. 28, 1986, incorporatedherein by reference. Useful succinic acid builders include the C5-C20alkyl succinic acids and salts thereof. A particularly preferredcompound of this type is dodecenylsuccinic acid. Alkyl succinic acidstypically are of the general formula R—CH(COOH)CH₂(COOH) i.e.,derivatives of succinic acid, wherein R is hydrocarbon, e.g., C₁₀-C₂₀alkyl or alkenyl, preferably C₁₂-C₁₆ or wherein R may be substitutedwith hydroxyl, sulfo, sulfoxy or sulfone substituents, all as describedin the above-mentioned patents.

The succinate builders are preferably used in the form of theirwater-soluble salts, including the sodium, potassium, ammonium andalkanolammonium salts.

Specific examples of succinate builders include laurylsuccinate,myristylsuccinate, palmitylsuccinate, 2-dodecenylsuccinate (preferred),2-pentadecenylsuccinate, and the like. Laurylsuccinates are thepreferred builders of this group, and are described in European PatentApplication 86200690.5/0 200 263, published Nov. 5, 1986.

Examples of useful builders also include sodium and potassiumcarboxymethyloxymalonate, carboxymethyloxysuccinate,cis-cyclo-hexanehexacarboxylate, cis-cyclopentane-tetracarboxylate,water-soluble polyacrylates and the copolymers of maleic anhydride withvinyl methyl ether or ethylene.

Other suitable polycarboxylates are the polyacetal carboxylatesdisclosed in U.S. Pat. No. 4,144,226, Crutchfield et al., issued Mar.13, 1979, incorporated herein by reference. These polyacetalcarboxylates can be prepared by bringing together, under polymerizationconditions, an ester of glyoxylic acid and a polyerization initiator.The resulting polyacetal carboxylate ester is then attached tochemically stable end groups to stabilize the polyacetal carboxylateagainst rapid depolymerization in alkaline solution, converted to thecorresponding salt, and added to a surfactant.

Polycarboxylate builders are also disclosed in U.S. Pat. No. 3,308,067,Diehl, issued Mar. 7, 1967, incorporated herein by reference. Suchmaterials include the water-soluble salts of homo- and copolymers ofaliphatic carboxylic acids such as maleic acid, itaconic acid, mesaconicacid, fumaric acid, aconitic acid, citraconic acid and methylenemalonicacid.

Suitable polyphosphonates for use herein are the alkali metal, ammoniumand alkanolammonium salts of polyphosphates (exemplified by thetripolyphosphates, pyrophosphates, and glassy polymericmeta-phosphates), phosphonates. The most preferred builder for useherein is citrate.

Divalent Ions:

The compositions according to the present invention may further comprisea divalent ion, or mixtures thereof. All divalent ions known to thoseskilled in the art may be used herein. Preferred divalent ions to beused herein are calcium, zinc, cadmium, nickel, copper, cobalt,zirconium, chromium and/or magnesium and more preferred are calcium,zinc and/or magnesium. Said divalent ions may be added in the form ofsalts for example as chloride, acetate, sulphate, formate and/or nitrateor as a complex metal salt. For example, calcium may be added in theform of calcium chloride, magnesium as magnesium acetate or magnesiumsulphate and zinc as zinc chloride. Typically such ions may be presentat a level up to 3%, preferably from 0.001% to 1% by weight of the totalcomposition.

Other Antiresoiling Ingredients:

The compositions of the present invention particularly suitable for thecleaning of a hard-surface may comprise another antiresoiling ingredienton top of the polyalkoxylene glycol diester and polyvinyl homopolymer orcopolymer as described herein before. Suitable additional antiresoilingingredients for use herein include those selected from the groupconsisting of polyalkoxylene glycol, mono- and dicapped polyalkoxyleneglycol and a mixture thereof, as defined herein after. The compositionsof the present invention may comprise up to 20% by weight of the totalcomposition of such another antiresoiling ingredient or a mixturethereof, preferably from 0.01% to 10%, more preferably from 0.1% to 5%and most preferably from 0.2% to 2%.

Suitable polyalkoxylene glycols for use herein are according to thefollowing formula H—O—(CH₂—CHR₂O)_(n)—H.

Suitable monocapped polyalkoxylene glycols for use herein are accordingto the following formula R₁—O—(CH₂—CHR₂O)_(n)—H.

Suitable dicapped polyalkoxylene glycols for use herein are according tothe formula R₁—O—(CH₂—CHR₂O)_(n)—R₃.

In these formulas the substituents R₁ and R₃ each independently aresubstituted or unsubstituted, saturated or unsaturated, linear orbranched hydrocarbon chains having from 1 to 30 carbon atoms, or aminobearing linear or branched, substituted or unsubstituted hydrocarbonchains having from 1 to 30 carbon atoms, R₂ is hydrogen or a linear orbranched hydrocarbon chain having from 1 to 30 carbon atoms, and n is aninteger greater than 0.

Preferably R₁ and R₃ each independently are substituted orunsubstituted, linear or branched alkyl groups, alkenyl groups or arylgroups having from 1 to 30 carbon atoms, preferably from 1 to 16, morepreferably from 1 to 8 and most preferably from 1 to 4, or amino bearinglinear or branched, substituted or unsubstituted alkyl groups, alkenylgroups or aryl groups having from 1 to 30 carbon atoms, more preferablyfrom 1 to 16, even more preferably from 1 to 8 and most preferably from1 to 4. Preferably R₂ is hydrogen, or a linear or branched alkyl group,alkenyl group or aryl group having from 1 to 30 carbon atoms, morepreferably from 1 to 16, even more preferably from 1 to 8, and mostpreferably R₂ is methyl, or hydrogen. Preferably n is an integer greaterthan 1, more preferably from 5 to 1000, more preferably from 10 to 100,even more preferably from 20 to 60 and most preferably from 30 to 50.

The preferred polyalkoxylene glycols, mono and dicapped polyalkoxyleneglycols to be used herein have a molecular weight of at least 200, morepreferably from 400 to 5000 and most preferably from 800 to 3000.

Suitable monocapped polyalkoxylene glycols for use herein include2-aminopropyl polyethylene glycol (MW 2000), methyl polyethylene glycol(MW 1800) and the like. Such monocapped polyalkoxylene glycols may becommercially available from Hoescht under the polyglycol series orHunstman under the tradename XTJ®. Suitable polyalkoxylene glycols to beused herein are polyethylene glycols like polyethylene glycol (MW 2000).

Suitable dicapped polyalkoxylene glycols for use herein includeO,O′-bis(2-aminopropyl)polyethylene glycol (MW 2000),O,O′-bis(2-aminopropyl)polyethylene glycol (MW 400), O,O′-dimethylpolyethylene glycol (MW 2000), dimethyl polyethylene glycol (MW 2000),or mixtures thereof. A preferred dicapped polyalkoxylene glycol for useherein is dimethyl polyethylene glycol (MW 2000). For instance dimethylpolyethylene glycol may be commercially available from Hoescht as thepolyglycol series, e.g. PEG DME-2000, or from Huntsman under the nameJeffamine® and XTJ®.

These polyalkoxylene glycols, mono- or dicapped polyalkoxylene glycolscontribute to the benefit of the liquid hard-surface compositions of thepresent invention, i.e. they help further improving the next-timecleaning performance of the composition herein. Dicapped polyalkoxyleneglycols are highly preferred herein.

Suds Controlling Agents:

The compositions according to the present invention may further comprisea suds controlling agent such as 2-alkyl alkanol, or mixtures thereof,as a preferred optional ingredient. Particularly suitable to be used inthe present invention are the 2-alkyl alkanols having an alkyl chaincomprising from 6 to 16 carbon atoms, preferably from 8 to 12 and aterminal hydroxy group, said alkyl chain being substituted in the aposition by an alkyl chain comprising from 1 to 10 carbon atoms,preferably from 2 to 8 and more preferably 3 to 6. Such suitablecompounds are commercially available, for instance, in the Isofol®series such as Isofol® 12 (2-butyl octanol) or Isofol® 16 (2-hexyldecanol).

Other suds controlling agents may include alkali metal (e.g., sodium orpotassium) fatty acids, or soaps thereof, containing from about 8 toabout 24, preferably from about 10 to about 20 carbon atoms.

The fatty acids including those used in making the soaps can be obtainedfrom natural sources such as, for instance, plant or animal-derivedglycerides (e.g., palm oil, coconut oil, babassu oil, soybean oil,castor oil, tallow, whale oil, fish oil, tallow, grease, lard andmixtures thereof. The fatty acids can also be synthetically prepared(e.g., by oxidation of petroleum stocks or by the Fischer-Tropschprocess).Alkali metal soaps can be made by direct saponification of fatsand oils or by the neutralization of the free fatty acids which areprepared in a separate manufacturing process. Particularly useful arethe sodium and potassium salts of the mixtures of fatty acids derivedfrom coconut oil and tallow, i.e., sodium and potassium tallow andcoconut soaps. The term “tallow” is used herein in connection with fattyacid mixtures which typically have an approximate carbon chain lengthdistribution of 2.5% C14, 29% C16, 23% C18, 2% palmitoleic, 41.5% oleicand 3% linoleic (the first three fatty acids listed are saturated).Other mixtures with similar distribution, such as the fatty acidsderived from various animal tallows and lard, are also included withinthe term tallow. The tallow can also be hardened (i.e., hydrogenated) toconvert part or all of the unsaturated fatty acid moieties to saturatedfatty acid moieties. When the term “coconut” is used herein it refers tofatty acid mixtures which typically have an approximate carbon chainlength distribution of about 8% C8, 7% C10, 48% C12, 17% C14, 9% C16, 2%C18, 7% oleic, and 2% linoleic (the first six fatty acids listed beingsaturated). Other sources having similar carbon chain lengthdistribution such as palm kernel oil and babassu oil are included withthe term coconut oil.

Other suitable suds controlling agents are exemplified by silicones, andsilica-silicone mixtures. Silicones can be generally represented byalkylated polysiloxane materials while silica is normally used in finelydivided forms exemplified by silica aerogels and xerogels andhydrophobic silicas of various types. These materials can beincorporated as particulates in which the suds controlling agent isadvantageously releasably incorporated in a water-soluble orwater-dispersible, substantially non-surface-active detergentimpermeable carrier. Alternatively the suds controlling agent can bedissolved or dispersed in a liquid carrier and applied by spraying on toone or more of the other components.

A preferred silicone suds controlling agent is disclosed in Bartollotaet al. U.S. Pat. No. 3,933,672. Other particularly useful sudscontrolling agents are the self-emulsifying silicone suds controllingagents, described in German Patent Application DTOS 2 646 126 publishedApr. 28, 1977. An example of such a compound is DC-544, commerciallyavailable from Dow Corning, which is a siloxane-glycol copolymer.

Especially preferred silicone suds controlling agents are described inCopending European Patent application No. 92201649.8. Said compositionscan comprise a silicone/silica mixture in combination with fumednonporous silica such as Aerosil®.

Especially preferred suds controlling agent are the suds controllingagent system comprising a mixture of silicone oils and the2-alkyl-alcanols.

Typically, the compositions herein may comprise up to 4% by weight ofthe total composition of a suds controlling agent, or mixtures thereof,preferably from 0.1% to 1.5% and most preferably from 0.1% to 0.8%.

Solvents

The compositions of the present invention may further comprise a solventor a mixtures thereof. Solvents for use herein include all those knownto the those skilled in the art of hard-surfaces cleaner compositions.Suitable solvents for use herein include ethers and diethers having from4 to 14 carbon atoms, preferably from 6 to 12 carbon atoms, and morepreferably from 8 to 10 carbon atoms, glycols or alkoxylated glycols,alkoxylated aromatic alcohols, aromatic alcohols, aliphatic branchedalcohols, alkoxylated aliphatic branched alcohols, alkoxylated linearC1-C5 alcohols, linear C1-C5 alcohols, C8-C14 alkyl and cycloalkylhydrocarbons and halohydrocarbons, C6-C16 glycol ethers and mixturesthereof.

Suitable glycols to be used herein are according to the formulaHO—CR1R2—OH wherein R1 and R2 are independently H or a C2-C10 saturatedor unsaturated aliphatic hydrocarbon chain and/or cyclic. Suitableglycols to be used herein are dodecaneglycol and/or propanediol.

Suitable alkoxylated glycols to be used herein are according to theformula R—(A)n—R1—OH wherein R is H, OH, a linear saturated orunsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to 15and more preferably from 2 to 10, wherein R1 is H or a linear saturatedor unsaturated alkyl of from 1 to 20 carbon atoms, preferably from 2 to15 and more preferably from 2 to 10, and A is an alkoxy group preferablyethoxy, methoxy, and/or propoxy and n is from 1 to 5, preferably 1 to 2.Suitable alkoxylated glycols to be used herein are methoxy octadecanoland/or ethoxyethoxyethanol.

Suitable alkoxylated aromatic alcohols to be used herein are accordingto the formula R(A)_(n)—OH wherein R is an alkyl substituted ornon-alkyl substituted aryl group of from 1 to 20 carbon atoms,preferably from 2 to 15 and more preferably from 2 to 10, wherein A isan alkoxy group preferably butoxy, propoxy and/or ethoxy, and n is aninteger of from 1 to 5, preferably 1 to 2.

Suitable alkoxylated aromatic alcohols are benzoxyethanol and/orbenzoxypropanol.

Suitable aromatic alcohols to be used herein are according to theformula R—OH wherein R is an alkyl substituted or non-alkyl substitutedaryl group of from 1 to 20 carbon atoms, preferably from 1 to 15 andmore preferably from 1 to 10. For example a suitable aromatic alcohol tobe used herein is benzyl alcohol.

Suitable aliphatic branched alcohols to be used herein are according tothe formula R—OH wherein R is a branched saturated or unsaturated alkylgroup of from 1 to 20 carbon atoms, preferably from 2 to 15 and morepreferably from 5 to 12. Particularly suitable aliphatic branchedalcohols to be used herein include 2-ethylbutanol and/or2-methylbutanol.

Suitable alkoxylated aliphatic branched alcohols to be used herein areaccording to the formula R(A)_(n)—OH wherein R is a branched saturatedor unsaturated alkyl group of from 1 to 20 carbon atoms, preferably from2 to 15 and more preferably from 5 to 12, wherein A is an alkoxy grouppreferably butoxy, propoxy and/or ethoxy, and n is an integer of from 1to 5, preferably 1 to 2. Suitable alkoxylated aliphatic branchedalcohols include 1-methylpropoxyethanol and/or 2-methylbutoxyethanol.

Suitable alkoxylated linear C1-C5 alcohols to be used herein areaccording to the formula R(A)_(n)—OH wherein R is a linear saturated orunsaturated alkyl group of from 1 to 5 carbon atoms, preferably from 2to 4, wherein A is an alkoxy group preferably butoxy, propoxy and/orethoxy, and n is an integer of from 1 to 5, preferably 1 to 2. Suitablealkoxylated aliphatic linear C1-C5 alcohols are butoxy propoxy propanol(n-BPP), butoxyethanol, butoxypropanol, ethoxyethanol or mixturesthereof. Butoxy propoxy propanol is commercially available under thetrade name n-BPP® from Dow chemical.

Suitable linear C1-C5 alcohols to be used herein are according to theformula R—OH wherein R is a linear saturated or unsaturated alkyl groupof from 1 to 5 carbon atoms, preferably from 2 to 4. Suitable linearC1-C5 alcohols are methanol, ethanol, propanol or mixtures thereof.

Other suitable solvents include butyl diglycol ether (BDGE),butyltriglycol ether, ter amilic alcohol and the like. Particularlypreferred solvents to be used herein are butoxy propoxy propanol, butyldiglycol ether, benzyl alcohol, butoxypropanol, ethanol, methanol,isopropanol and mixtures thereof.

Typically, the compositions of the present invention comprise up to 20%by weight of the total composition of a solvent or mixtures thereof,preferably from 0.5% to 10% by weight and more preferably from 1% to 8%.

Bleaching Components

The liquid compositions herein may also comprise a bleaching component.Any bleach known to those skilled in the art may be suitable to be usedherein including any peroxygen bleach as well as a chlorine releasingcomponent.

Suitable peroxygen bleaches for use herein include hydrogen peroxide orsources thereof. As used herein a source of hydrogen peroxide refers toany compound which produces active oxygen when said compound is incontact with water. Suitable water-soluble sources of hydrogen peroxidefor use herein include percarbonates, preformed percarboxylic acids,persilicates, persulphates, perborates, organic and inorganic peroxidesand/or hydroperoxides.

Suitable chlorine releasing component for use herein is an alkali metalhypochlorite. Advantageously, the composition of the invention arestable in presence of this bleaching component. Although alkali metalhypochlorites are preferred, other hypochlorite compounds may also beused herein and can be selected from calcium and magnesium hypochlorite.A preferred alkali metal hypochlorite for use herein is sodiumhypochlorite.

Bleach Activators

The compositions of the present invention that comprise a peroxygenbleach may further comprise a bleach activator or mixtures thereof. By“bleach activator”, it is meant herein a compound which reacts withperoxygen bleach like hydrogen peroxide to form a peracid. The peracidthus formed constitutes the activated bleach. Suitable bleach activatorsto be used herein include those belonging to the class of esters,amides, imides, or anhydrides. Examples of suitable compounds of thistype are disclosed in British Patent GB 1 586 769 and GB 2 143 231 and amethod for their formation into a prilled form is described in EuropeanPublished Patent Application EP-A-62 523. Suitable examples of suchcompounds to be used herein are tetracetyl ethylene diamine (TAED),sodium 3,5,5 trimethyl hexanoyloxybenzene sulphonate, diperoxydodecanoic acid as described for instance in U.S. Pat. No. 4,818,425 andnonylamide of peroxyadipic acid as described for instance in U.S. Pat.No. 4,259,201 and n-nonanoyloxybenzenesulphonate (NOBS). Also suitableare N-acyl caprolactams selected from the group consisting ofsubstituted or unsubstituted benzoyl caprolactam, octanoyl caprolactam,nonanoyl caprolactam, hexanoyl caprolactam, decanoyl caprolactam,undecenoyl caprolactam, formyl caprolactam, acetyl caprolactam,propanoyl caprolactam, butanoyl caprolactam pentanoyl caprolactam ormixtures thereof. A particular family of bleach activators of interestwas disclosed in EP 624 154, and particularly preferred in that familyis acetyl triethyl citrate (ATC). Acetyl triethyl citrate has theadvantage that it is environmental-friendly as it eventually degradesinto citric acid and alcohol. Furthermore, acetyl triethyl citrate has agood hydrolytical stability in the product upon storage and it is anefficient bleach activator. Finally, it provides good building capacityto the composition.

Packaging form of the Compositions

The compositions herein may be packaged in a variety of suitabledetergent packaging known to those skilled in the art. The liquidcompositions are preferably packaged in conventional detergent plasticbottles.

In one embodiment the compositions herein may be packaged in manuallyoperated spray dispensing containers, which are usually made ofsynthetic organic polymeric plastic materials. Accordingly, the presentinvention also encompasses liquid cleaning compositions of the inventionpackaged in a spray dispenser, preferably in a trigger spray dispenseror pump spray dispenser.

Indeed, said spray-type dispensers allow to uniformly apply to arelatively large area of a surface to be cleaned the liquid cleaningcompositions suitable for use according to the present invention. Suchspray-type dispensers are particularly suitable to clean verticalsurfaces.

Suitable spray-type dispensers to be used according to the presentinvention include manually operated foam trigger-type dispensers soldfor example by Specialty Packaging Products, Inc. or ContinentalSprayers, Inc. These types of dispensers are disclosed, for instance, inU.S. Pat. No. 4,701,311 to Dunnining et al. and U.S. Pat. No. 4,646,973and U.S. Pat. No. 4,538,745 both to Focarracci. Particularly preferredto be used herein are spray-type dispensers such as T 8500® commerciallyavailable from Continental Spray International or T 8100® commerciallyavailable from Canyon, Northern Ireland. In such a dispenser the liquidcomposition is divided in fine liquid droplets resulting in a spray thatis directed onto the surface to be treated. Indeed, in such a spray-typedispenser the composition contained in the body of said dispenser isdirected through the spray-type dispenser head via energy communicatedto a pumping mechanism by the user as said user activates said pumpingmechanism. More particularly, in said spray-type dispenser head thecomposition is forced against an obstacle, e.g. a grid or a cone or thelike, thereby providing shocks to help atomise the liquid composition,i.e. to help the formation of liquid droplets.

The Process of Cleaning a Hard-surface:

The present invention also encompasses a process of cleaninghard-surfaces wherein a liquid composition comprising a polyalkoxyleneglycol diester and a vinylpyrrolidone homopolymer or copolymer asdescribed herein before, is contacted with said surfaces.

By “hard-surfaces”, it is meant herein any kind of surfaces typicallyfound in houses like kitchens, bathrooms, or in car interiors orexteriors, e.g., floors, walls, tiles, windows, sinks, showers, showerplastified curtains, wash basins, WCs, dishes, fixtures and fittings andthe like made of different materials like ceramic, vinyl, no-wax vinyl,linoleum, melamine, glass, any plastics, plastified wood, metal or anypainted or varnished or sealed surface and the like. Hard-surfaces alsoinclude household appliances including, but not limited to,refrigerators, freezers, washing machines, automatic dryers, ovens,microwave ovens, dishwashers and so on.

The liquid compositions of the present invention may be contacted to thesurface to be cleaned in its neat form or in its diluted form.

By “diluted form” it is meant herein that said liquid composition isdiluted by the user typically with water. The composition is dilutedprior use to a typical dilution level of 10 to 400 times its weight ofwater, preferably from 10 to 200 and more preferably from 10 to 100.Usual recommended dilution level is a 1.2% dilution of the compositionin water.

In the preferred process of cleaning hard-surfaces according to thepresent invention where said composition is used in diluted form, thereis no need to rinse the surface after application of the composition inorder to obtain excellent first and next-time cleaning performance andalso excellent end result surface appearance.

THE PRESENT INVENTION WILL BE FURTHER ILLUSTRATED BY THE FOLLOWINGEXAMPLES. EXAMPLES

The following compositions were made by mixing the listed ingredients inthe listed proportions. All proportions are % by weight of the totalcomposition. Excellent first and next-time cleaning performance and goodgloss were delivered to the hard-surfaces cleaned with thesecompositions both under neat and diluted conditions, e.g. at a dilutionlevel of 50:1 to 200:1 (water: composition).

Compositions (weight %): A B C D E F Nonionic surfactants C 9-11 EO5 2.41.9 2.5 — — 2.5 C12, 14 EO5 3.6 2.9 2.5 2.5 — 2.5 C7-9 EO6 — — — — 3.2 —Dobanol ® 23-3 — — — — 1.3 — AO21 1.0 0.8 4.0 — 1.9 2.0 Anionicsurfactants NaPS — — — — — — NaLAS — — — 4.0 0.9 0.8 NaCS 1.5 2.6 — 2.31.2 1.5 C₈-AS — — — — 0.8 — Isalchem ® AS 0.6 0.6 — — — — Buffer Na₂CO₃0.6 0.13 0.6 1.0 1.0 0.1 Citrate 0.5 0.56 0.5 — — 0.6 Caustic 0.3 0.330.3 — — 0.3 Suds control Fatty Acid 0.6 0.3 0.5 0.4 0.4 0.5 Isofol 12 ®0.3 0.3 — 0.3 0.3 0.3 Polymers Kessco 6000DS ® 0.4 — 0.3 — 0.5 0.35Marlosol FS ® — 0.4 — 0.5 — — PVP K60 ® — — — 0.5 — — PVP K90 ® 0.3 0.40.6 — 0.5 0.3 Minors and water ----- up to 100% ----- pH 9.5 7.4 9.510.5 10.75 7.5 G H I J K L M Nonionic surfactants C 9-11 EO5 — — 2.5 2.4— 2.5 0.030 C12, 14 EO5 — — 2.5 3.6 — 2.5 0.030 C7-9 EO6 3.2 8 — — 3.2 —— Dobanol ® 23-3 1.3 3.2 — — 1.3 — — AO21 1.9 4.8 2.0 1.0 1.9 2.0 0.024Anionic surfactants NaPS — 3.0 — — — — — NaLAS 0.9 — 0.8 — 0.9 0.8 0.009NaCS 1.2 3.0 1.5 1.5 1.2 1.5 0.018 C₈-AS 0.8 2.0 — — 0.8 — — Isalchem ®AS — — — 0.6 — — — Buffer Na₂CO₃ 1.0 2.0 0.2 0.6 1.0 0.2 0.002 Citrate —— 0.75 0.5 — 0.75 0.009 Caustic — — 0.5 0.3 — 0.5 0.006 Suds controlFatty Acid 0.4 0.8 0.4 0.6 0.4 0.4 0.005 Isofol 12 ® 0.3 — 0.3 0.3 0.30.3 0.004 Polymers Kessco 6000DS ® 0.5 0.75 0.5 0.5 0.5 0.4 0.006 PVPK90 ® — 0.5 0.5 — — 0.3 0.006 PVP K60 ® 0.5 — — 0.5 0.5 — — Minors andwater ----- up to 100% ----- pH 10.7 10.75 9.5 9.5 10.75 9.5 8.5

PVP K60® and PVP K90® are vinylpyrrolidone homopolymers (averagemolecular weight of 160,000), commercially available from ISPCorporation, New York, N.Y. and Montreal, Canada.

Kessco 600ODS® is O,O′-distearyl polyethylene glycol diestercommercially available from Akzo Nobel.

Marlosol FS® is O,O′-dioleyl polyethylene glycol diester commerciallyavailable from Huls.

Isofol® is 2-butyl octanol

Dobanol® 23-3 is a C12-C13 EO 3 nonionic surfactant commerciallyavailable from SHELL.

C8-AS is octyl sulphate available from Albright and Wilson, under thetradename Empimin® LV 33.

AO21 is a C12-14 EO21 alcohol ethoxylate.

Isalchem® as is a branched alcohol alkyl sulphate commercially availablefrom enichem.

What is claimed is:
 1. An aqueous liquid hard-surface cleaningcomposition comprising a polyalkoxylene glycol diester according to theformula:

wherein the substituents R1 and R2 each independently are substituted orunsubstituted, saturated or unsaturated, linear or branched hydrocarbonchains having from 1 to 36 carbon atoms and wherein n is an integer from10 to 400, and a vinylpyrrolidone homopolymer or copolymer; saidcomposition having a pH of from about 1 to about
 13. 2. A compositionaccording to claim 1 which comprises from about 0.001% to about 20% byweight of the total composition of the polyalkoxylene glycol diester ora mixture thereof.
 3. A composition according to claim 2 which comprisesfrom about 0.01% to about 10% by weight of the total composition of thepolyalkoxylene glycol diester or a mixture thereof.
 4. A compositionaccording to claim 2 which comprises from about 0.1% to about 5% byweight of the total composition of the polyalkoxylene glycol diester ora mixture thereof.
 5. A composition according to claim 2 which comprisesfrom about 0.2% to about 2% by weight of the total composition of thepolyalkoxylene glycol diester or a mixture thereof.
 6. A compositionaccording to claim 1 wherein in said polyalkoxylene glycol diester, thesubstituents R₁ and R₂ each independently are substituted orunsubstituted, linear or branched alkyl groups or alkenyl groups havingfrom about 1 to about 36 carbon atoms, or aryl groups having up to about36 carbon atoms, and wherein n is an integer from about 20 to about 400.7. A composition according to claim 1 wherein said polyalkoxylene glycoldiester is O,O′-distearyl polyethylene glycol diester, O,O′-dioleylpolyethylene glycol diester or a mixture thereof.
 8. A compositionaccording to claim 1 which comprises from about 0.001% to about 20% byweight of the total composition of vinylpyrrolidone homopolymer orcopolymer or a mixture thereof.
 9. A composition according to claim 8which comprises from about 0.01% to about 10% by weight of the totalcomposition of vinylpyrrolidone homopolymer or copolymer or a mixturethereof.
 10. A composition according to claim 8 which comprises fromabout 0.1% to about 5% by weight of the total composition ofvinylpyrrolidone homopolymer or copolymer or a mixture thereof.
 11. Acomposition according to claim 8 which comprises from about 0.2% toabout 2% by weight of the total composition of vinylpyrrolidonehomopolymer or copolymer or a mixture thereof.
 12. A compositionaccording to claim 1 wherein said vinylpyrrolidone homopolymer is anhomopolymer of N-vinylpyrrolidone having the following repeatingmonomer:

wherein n is an integer of from about 10 to about 1,000,000.
 13. Acomposition according to claim 1 which has a pH of from about 7 to about12.
 14. A composition according to claim 1 which has a pH of from about9 to about
 11. 15. A composition according to claim 1 which comprises anoptional ingredient selected from the group consisting of surfactants,builders, chelants, polymers, solvents, buffers, bactericides,hydrotropes, colorants, stabilisers, radical scavengers, bleaches,bleach activators, fatty acids, enzymes, soil suspenders, dye transferagents, brighteners, anti dusting agents, suds controlling agents,dispersants, dye transfer inhibitors, pigments, dyes, perfumes andmixtures thereof.
 16. A composition according to claim 15 wherein saidsurfactant is selected from the group consisting of non ionicsurfactants, anionic surfactants, zwitterionic surfactants, amphotericsurfactants, cationic surfactants and mixtures thereof and is present ata level of from about 0.1% to about 50% by weight of the totalcomposition.
 17. A composition according to claim 16 wherein saidsurfactant is present at a level of from about 0.1% to about 20% byweight of the total composition.
 18. A composition according to claim 16wherein said surfactant is present at a level of from about 1% to about10% by weight of the total composition.
 19. A process of cleaning ahard-surface wherein a liquid composition according to claim 1, iscontacted with said surface.
 20. A process of cleaning a hard-surfaceaccording to claim 19 wherein said composition is contacted with saidsurface after having been diluted with water.
 21. A process according toclaim 20 wherein said surface is not rinsed after said composition hasbeen contacted with said surface.